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Life on our planet likely evolved in the ocean, and thus exo-oceans are key habitats to search for extraterrestrial life. We conducted a data-driven bibliographic survey on the astrobiology literature to identify emerging research trends with marine science for future synergies in the exploration for extraterrestrial life in exo-oceans. Based on search queries, we identified 2592 published items since 1963. The current literature falls into three major groups of terms focusing on (1) the search for life on Mars, (2) astrobiology within our Solar System with reference to icy moons and their exo-oceans, and (3) astronomical and biological parameters for planetary habitability. We also identified that the most prominent research keywords form three key-groups focusing on (1) using terrestrial environments as proxies for Martian environments, centred on extremophiles and biosignatures, (2) habitable zones outside of "Goldilocks" orbital ranges, centred on ice planets, and (3) the atmosphere, magnetic field, and geology in relation to planets' habitable conditions, centred on water-based oceans. [ABSTRACT FROM AUTHOR]

Chemical and structural complexities in interstratified clay minerals arising from mineral transformations and evolving formation conditions should be recorded in their stable isotope signatures. This paper examines the controls on the stable hydrogen and oxygen isotope compositions of Fe3+-rich, glauconite-nontronite, talc-nontronite and talc-saponite from submarine hydrothermal sites, with a focus on the Red Sea Atlantis II Deep. Values of δ 18O became less positive in the order nontronite > glauconite-nontronite > talc-nontronite > talc-saponite, yielding oxygen isotope temperatures ranging from ∼40 °C for nontronite to ∼135–300 °C for talc-saponite. These clay minerals have low δ 2H, ranging from −145 to −127‰ for talc-nontronite, −135‰ for nontronite, −129 to −85‰ for glauconite-nontronite, and −95 to −59‰ for talc-saponite. The clay mineral-water hydrogen isotope fractionation is strongly affected by Fe3+ content, with increasing structural Fe3+ causing progressive weakening of O-H bonds. The large ionic radius and high charge of Fe3+ cause it to be more poorly shielded by surrounding oxygen from hydroxyl hydrogen relative to other octahedral or tetrahedral cations. The resulting lengthening of O-H bonds favours 1H over 2H. Our results confirm that Fe-rich phases, such as nontronite-glauconite, are produced at the lowest temperatures and Mg-rich phases, such as talc-saponite, are formed at the highest temperatures in seafloor hydrothermal environments. Evolving fluid chemistry and fluid pathways during clay mineral formation are also important. Glauconite layer formation from precursor nontronite likely occurred during diagenesis; redox changes causing Fe-reduction and an increase in layer charge facilitated interlayer K-fixation. Talc-saponite compositions vary with temperature and fluid chemistry, forming at variable sediment depths depending on access to the hottest hydrothermal fluids. • Fe3+ content controls δ 2H OH of seafloor Fe-rich hydrothermal, interstratified clay. • Large ionic radius and high charge of Fe3+ causes systematic decrease in clay δ 2H. • Seafloor clay δ 18O indicates lower temperature formation of Fe- versus Mg-rich phases. • Diagenetic glauconite-nontronite formed at ∼75 °C (Atlantis II Deep) from nontronite. • Talc-nontronite formed at ∼95 °C and talc-saponite at ∼240 °C (Atlantis II Deep). [ABSTRACT FROM AUTHOR]

Keywords: Phyllosilicates; glauconite; nontronite; peak shift EN Phyllosilicates glauconite nontronite peak shift 1080 1090 11 06/01/22 20220601 NES 220601 Introduction Raman spectroscopy found widespread application in the rapid and non-destructive characterization of silicate minerals ([26]; [8]; [35]; [34]; [44]; [31]; [1]; [45], 2015; [30]). Concluding remarks In this study, Raman spectroscopy analysis of nontronite and glauconite-nontronite mixed-layer phases from deep-sea hydrothermal fields reveals that these phyllosilicates have diagnostic Raman spectral features that include a series of strong peaks in the low wavenumber region (<700 cm SP -1 sp ) and the hydroxyl domain (3500-3700 cm SP -1 sp ). To fill these knowledge gaps, this study reports a comprehensive Raman spectral characterization of nontronite and glauconite-nontronite mixed-layer phases (i.e., vertical mixing/interstratification of glauconite and nontronite layers) from seafloor hydrothermal fields. Chemistry/structure-dependent Raman spectral features of glauconite and nontronite For the analyzed nontronite and glauconite-nontronite mixed-layer samples, the covariations between Raman spectral properties and octahedral chemistry (Table 2; Figs. [Extracted from the article]

The environmental availability of mineral nutrients plays a role in the adaptation and evolution of soil fungi and fungus-plant symbiotic systems. As nutrient availability is different from soil to soil, it is expected that the most adapted fungi can express multiple genes to promote different mechanisms of mineral attack and of metabolic routes to maximize the use of nutrient resources at the lowest energy cost. Microcosm experiments of Paxillus involutus growing on muscovite, phlogopite and K-exchanged vermiculite as K sources were carried out for 21 days. Gene expression analysis indicated that the level of K-deprivation stress was muscovite > phlogopite ≫ K-vermiculite. Genes and functions overexpressed in the experiments indicated meaningful metabolic activities including K extraction and transport. SEM-EDS and micro-XRD (∼1.15 mm resolution) analysis of mineral surfaces and chemical analysis of agar and mycelium indicated weathering processes and K uptake in good agreement with gene expression analysis. In many areas, P. involutus caused physical damage to the minerals without any apparent chemical attack, consisting of tracks of different depth, from <1 μm to ∼80 μm wide, and piles of removed material. However, all minerals were partly dissolved. Phlogopite and vermiculite presented cation-depleted areas, but not muscovite. The dissolution trends of phlogopite and vermiculite were similar, with loss of K, Al and Mg, and concentration of Si, Ti and Fe, although Si and Fe were also lost with respect to Ti. The different mobilization of Al and Fe is noteworthy. Release of K from vermiculite by cation exchange was extensive, both abiotic and driven by P. involutus. The experimental conditions closest to most environmental situations are those in K-vermiculite tests. The results provide a new and coherent insight into fungal adaptation to mineral nutrient stress where fungal activity was regulated by both K requirement and success of the actions to secure it. [ABSTRACT FROM AUTHOR]

Fe(II) only occupies octahedral sites in phyllosilicates, whereas Fe(III) can occupy both octahedral and tetrahedral sites. The controls on Fe(III) distribution between tetrahedral and octahedral sites have been a matter of great interest to understand the interplay between formation environment (Fe abundance, redox conditions) and crystal-chemical factors (stability of the crystal lattice) during crystallization of Fe-phyllosilicates. Here, for the first time, we present a model of Fe(III) distribution in 2:1 phyllosilicates. We investigated 21 samples of 2:1 phyllosilicates of submarine hydrothermal origin using XRD, chemical analysis, and Mössbauer spectroscopy (and other supporting techniques not presented here). An additional data set of 49 analyses of 2:1 phyllosilicates from the literature was also used. Overall, the data cover a wide range of dioctahedral and trioctahedral phyllosilicates, including end-member minerals and interstratified phases. Dioctahedral phyllosilicates have a steric control whereby tetrahedral Fe(III) is only allowed if at least five out of six octahedral atoms are larger than Al (typically Fe[III], Fe[II], Mg) that produces an expanded structure where tetrahedral sites can accommodate Fe(III). After this threshold, further Fe(III) atoms occupy tetrahedral sites preferentially (~73% of further Fe[III] atoms) over octahedral sites. In trioctahedral 2:1 phyllosilicates there is no steric hindrance to tetrahedral Fe(III) because the crystal dimensions are such that tetrahedral sites can accommodate Fe(III). On average, Fe(III) enters tetrahedral and octahedral sites in similar proportion, and the only apparent control on tetrahedral Fe(III) abundance is Fe(III) availability during crystallization. This model allows to predict Fe(III) distribution between structural sites, provides an avenue for further exploration of the thermodynamic stability of phyllosilicates using cationic size, and provides a tool to better describe stability/reactivity of Fe-rich phyllosilicates, the most reactive of phyllosilicates and very relevant in geochemical and biological processes. [ABSTRACT FROM AUTHOR]

Abstract Phyllosilicate minerals have the potential to be used as indicators of past environmental conditions and climate. However, the appropriate use of this tool requires that the origin of the phyllosilicates be ascertained to correspond to the age under investigation, as mineralogical changes postdating it would lead to wrong conclusions. The soft sandstone of the Ashdown Formation (south-central and southeaster UK) contains fine-grained Al-phyllosilicates of limited interlayer expandability that have been described by other authors as vermiculite, smectite, interstratified illite-vermiculite and interstratified illite-smectite. The origin of these mineral phases is not yet agreed, with some authors reporting them as detrital and some as authigenic, generated by the weathering of detrital mica in the sandstone. In order to investigate whether or not these fine-grained minerals are detrital, four samples of the sandstone of variable softness were studied because they most likely had different clay content and because the different clay content could be possibly due to differential weathering. Investigation of mineralogy (X-ray diffraction), chemistry (bulk and SEM-EDS microanalysis) and rock fabric (image analysis of SEM micrographs) indicated that the sandstone consists of quartz, microcline, albite, anorthite, muscovite/illite, kaolinite, interstratified illite-smectite and smectite, where smectite layers expand only partially. Kaolinite is mainly detrital. Rock hardness was controlled by quartz abundance in the original sediment, not by later weathering. Alteration of the investigated sandstone samples after deposition was limited but reaction models are compatible with partial (<10 wt%) alteration of muscovite/illite to illite-smectite and smectite, and of microcline and plagioclase to kaolinite. Analysis of mineralogical data of the fraction <2 μm of the Ashdown Formation from the literature is compatible with this interpretation and indicates that the range of muscovite/illite alteration to interstratified illite-smectite and smectite varied widely (0–45% in the <2 μm size fraction) depending on location and depth. Highlights • Hardness of Sandstone from the Ashdown Formation (UK) follows quartz/clay ratio. • Quartz/clay ratio changes are controlled first by sedimentation, then by diagenesis. • The sandstone contains expandable clays of disputed origin. • Mineralogy and reaction models suggest that the expandable clays are authigenic. [ABSTRACT FROM AUTHOR]

Abstract A range of phyllosilicate compositions have been detected spectroscopically on Mars, but the largest fraction by far corresponds to clay minerals rich in Fe and Mg. Given that most of our understanding of Martian clays comes from remote sensing data, it is critically important to explore the details of how compositional variation affects spectral features of phyllosilicates. The greatest efforts have focused so far on near-infrared (NIR) spectroscopy. Recently, ambiguities have been detected in the NIR spectra of 2:1 phyllosilicates with intermediate Fe Mg content that preclude mineral and chemical discrimination. Such ambiguities highlight the relevance of exploring the visible spectral range as a complementary tool to characterize Martian phyllosilicates precisely. This article reports the investigation of laboratory reflectance spectra (330–800 nm) from 34 Earth analogues of Martian phyllosilicates with a wide range of Mg Fe composition, including nontronite, celadonite and saponite end-members, as well as interstratified glauconite-nontronite, talc-nontronite, and talc-saponite. The spectra indicated the presence of Fe(III) by absorption modulations and a decrease in total reflectance, especially in samples with tetrahedral Fe(III). Absorption bands at 370 and 420 nm were diagnostic of octahedrically and tetrahedrally coordinated Fe(III), respectively. Band amplitudes in the second derivative of the Kubelka-Munk function correlated positively with Fe(III) content (R 2 > 0.8). Standard color analyses of the visible reflectance spectra under the CIE illuminant D65 indicated that the CIELAB color parameter a * 10 was positively correlated with tetrahedral Fe(III), b * 10 was positively correlated with octahedral Fe(III), and L * 10 was negatively correlated with Fe(III) in both structural sites. Because Fe(II) was in relatively low amount, it did not provide clear spectral evidence. Multiple regression models using the amplitude of the diagnostic absorption bands predicted well absolute Fe content in the phyllosilicates (R 2 = 0.89) and the ratio Fe/(Fe + Mg + Al) (R 2 = 0.84). CIELAB color parameters improved the prediction of total Fe (R 2 = 0.92) and the ratio Fe/(Fe + Mg + Al) (R 2 = 0.93). Application of these analyses to Martian data has challenges set by Fe oxide dust coating and spatial and spectral resolution. However, these results mark an avenue to develop testable tools using visible-wavelength spectral data from both satellite and lander probes to help establishing Fe content and mineral identification of Martian phyllosilicates. Highlights • Visible-range spectra of phyllosilicates shaped by Fe content and site occupancy. • Phyllosilicate Fe content is predicted well by 2nd-derivative and color analyses. • Vis spectra from Martian rocks with phyllosilicates comparable to lab spectra. • 2nd-derivative and color analyses hopeful tool to estimate Fe in Martian clays. [ABSTRACT FROM AUTHOR]

Earth analogs are indispensable to investigate mineral assemblages on Mars because they enable detailed analysis of spectroscopic data from Mars and aid environmental interpretation. Samples from four sites in the Iberian Pyrite Belt (El Villar, Calañas, Quebrantahuesos, and Tharsis) were investigated using mineralogical, chemical, and spectroscopic techniques, with a focus on clay minerals and alteration environments. They represent Earth analogs of areas on Mars that underwent acidic alteration. X‑ray diffraction and transmittance mid-infrared data indicate that the rocks were subjected to several degrees of acid alteration corresponding to assemblages characterized by the following mixtures: (1) illite, chlorite, interstratified chlorite-vermiculite, kaolinite-smectite, and kaolinite; (2) illite, kaolinite, and alunite; and (3) jarosite and goethite. According to mineral stability data, these three assemblages correspond to pH values 7–5, 5–3, and <3, respectively. The lack of goethite in the illite-kaolinitealunite assemblage suggests an alteration in reducing conditions. Illite was progressively dissolved by acidic alteration but is sufficiently resilient not to be diagnostic of the intensity of the alteration. Illite and kaolinite were the two most abundant phyllosilicate minerals observed, and the main reaction involving phyllosilicates was the alteration of illite to kaolinite. Mixed-layer phases appeared mainly in the mildest degree of acid alteration, with few exceptions. This suggests a transition from a mechanism dominated by transformation to a mechanism dominated by dissolution-precipitation as the intensity of the acid alteration increases. Our results highlight the sparse kaolinite–alunite occurrences on Mars as worthy of specific investigation. Acid alteration on Mars is expected to be patchy and/or consisting of fine alteration rims. Alunite occurrences on Mars in the absence of goethite may indicate an acid alteration in reducing conditions. Kaolinite produced through acid alteration on Mars is expected to exist mainly as an end-member phase of low crystallinity, which would enhance IR absorption and increase its visibility. [ABSTRACT FROM AUTHOR]

The two major components most frequently found in sediments near submarine hydrothermal fields are Fe oxides/oxyhydroxides and nontronite. Physico-chemical conditions in these environments vary from site to site and even within sites as the type and intensity of the hydrothermal activity change. The investigation of Fe oxides/oxyhydroxides and nontronite is helpful to constrain the specific conditions in which they formed or evolved, and thus to recreate the history of hydrothermal vents. Microbial activity is also involved in the formation of these mineral phases, which adds the interest of revealing processes at the interface of biological and inorganic phenomena. We investigated sediments from ten seafloor hydrothermal fields, most of them Recent sediments. They are rich in Fe oxides/oxyhydroxides and/or nontronite and/or Fe-talc. SEM analysis with energy-dispersive X-ray spectroscopy revealed many morphological types, among which vermicular habits are common, with chemical composition ranging frequently between Fe oxides/oxyhydroxides and nontronite. Smooth surfaces of the investigated particles correlates with high Fe/Si ratios, and rough surfaces with low Fe/Si ratios. This feature and the fact that many particles had chemical compositions (Si, Fe, Mn, Mg, Al) in a continuous line linking Fe oxide and nontronite are compatible with the in situ reaction of Fe oxides/oxyhydroxides as a frequent mechanism of nontronite formation. This process involves the reaction of Fe oxides/oxyhydroxides with either silica polymers adsorbed on their surface or Si-Fe amorphous phases precipitated on the same surface. However, it was not possible to establish a pseudomorphic replacement (of Fe oxides by nontronite) as no nontronite grains were found reproducing habits observed in grains with large proportion of Fe oxides/oxyhydroxides. All particle morphologies can have a range of surface roughness and composition. Chemical composition consistent with nontronite was represented mainly by small particles (< 1 μm) and flakes or veil-like habits. The frequent vermicular habit caused by precipitation on Fe-oxidizing bacteria was in line with previous findings indicating this as an important process of precipitating a wide range of Fe-Si phases. Overall, our data suggest that in situ replacement of Fe oxides/oxyhydroxides by nontronite takes place in all types of particles but that the replacement does not preserve the original particle morphology. [ABSTRACT FROM AUTHOR]

Mangrove soils have peculiar chemical and physical conditions generated by the variable water salinity, cyclic tidal changes and intense biological activity that produce complex clay suites. In this study, the crystal-chemical characteristics of clay minerals from two mangrove soils were investigated in detail to further our understanding of the processes taking place. The two Brazilian mangroves are from zones of contrasting climatic type and continental sediment character: (1) tropical wet climate area receiving highly weathered sediments (Bragança, Pará State) and (2) mild semiarid climate area supplied with a mixture of highly and moderately weathered sediments (Acaraú, Ceará State). The investigation of the 2–0.2 μm and < 0.2 μm size fractions of the soils using XRD, Mössbauer spectroscopy, chemical analysis of individual mineral grains (TEM-EDS) and bulk samples (XRF) showed mineral assemblages composed by endmember and mixed-layer clay minerals. Three to four mineral phases were detected by XRD in each sample such as kaolinite-smectite minerals (K-S), illite-smectite (I-S) and Fe-rich illite, suggesting a progressive transformation via mixed-layering from detrital kaolinite (unstable in mangrove soil conditions) to K-S and I-S minerals rich in smectite, and then to Fe-rich illite. The chemical characterization corroborates this gradual transformation: there is an enrichment in K, Fe and Mg at the expense of Al in all samples. A solid-state reaction explains the sequential transformation, where crystal-chemical changes take place without complete disruption of the lattice. There is evidence of octahedral Fe reduction during the illitization stage, showing the influence of a reducing environment, from decaying organic matter and bacterial activity, on the clay minerals. The increase in layer charge is balanced by K and NH 4 ions, abundant in the interstitial water. Superior Fe-rich illite contents in Acaraú mangrove, compared to Bragança mangrove, are explained by high inputs of 2:1 clays from sediment source areas inland. The above clay mineral reactions shed light on the role of clays and the interaction between minerals and biotic components in mangrove soils. In addition, these reactions may influence the cycle of major elements in coastal ecosystem surrounding mangroves. [ABSTRACT FROM AUTHOR]

Mineral weathering processes in soils are important controls on soil characteristics and on bio- and geochemical cycling. Elucidation of these processes and their mechanisms is crucial for understanding soil environments and their influence globally. An Umbric Podzol from the Falkland Islands was studied while investigating possible ways to counteract soil degradation and loss. The soil had lost the O, E, and Bs horizons through erosion, thus revealing the transitional B/C horizon, which grades into the underlying parent material. Samples were taken from the B/C surface and 5 cm below the surface, then analyzed with X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectroscopy, organic C and N analysis, analysis of extractable Fe and Al with the dithionitecitrate- bicarbonate and ammonium oxalate methods, and Fourier-transform infrared analysis. The soil fabric and mineralogy were compatible with derivation from sandstone rock. Clasts of heterogeneous mineral composition as well as loose material from disaggregated clasts were present. The soil had large proportions of quartz and albite, and minor amounts of muscovite, chlorite, plagioclase, feldspar, kaolinite, and non-diffracting Fe oxide (goethite and/or ferrihydrite). The most peculiar characteristic was a large component (~7 wt% of the bulk soil) of an amorphous (non-X-ray diffracting) silicate phase of small particle size (<1 µm), non-extractable, with heterogeneous composition. The average composition of this phase is similar to that of the bulk soil and approaches that of Al-Fe-rich smectite. The amorphous phase is not allophane or imogolite by any of the analyses carried out. The amorphous silicate phase is formed partly by the translocation of metals from O, E, and Bs horizons and partly by dissolution of the primary minerals of the B/C horizon, both of which precipitated in combination with low water mobility causing rapid saturation of the interstitial water. There are no reports of amorphous silicate phases with these characteristics or abundances from soils or other weathering environments. Thus, our observations indicate the existence of complex, successive weathering steps not yet identified that could be investigated in materials subjected to slow weathering such as the soil described here. [ABSTRACT FROM AUTHOR]

The efficient use of REE as tracers of weathering processes requires further data acquisition to establish robust connections between mechanisms, mineral assemblages and REE concentration patterns. Here, results are provided corresponding to rocks from four locations in the Iberian Pyrite Belt that were altered with different intensity by sulfuric fluids. The acidic alteration was mild (pH 5–7) in Calañas and El Villar, while strong (pH below 3 to 5) in Quebrantahuesos and Tharsis. The main REE reservoir before alteration were phyllosilicates (and plagioclase/feldspar in El Villar only). Mild alteration generated mainly kaolinite while illite and some plagioclase/feldspar were preserved. Mildly altered rocks approximately preserved the relative REE concentrations of their precursors, interpreted as indicating a low fluid/rock ratio environment where binding sites in minerals outnumbered those in fluids. Strong acid alteration produced alunite, jarosite, beudantite and goethite, with partial illite preservation. Where illite and/or goethite were major minerals, this alteration generated REE patterns enriched in light REE over heavy REE or did not modify the relative REE concentrations of the original rock. However, samples where REE concentrations were controlled by alunite or jarosite had LREE > > HREE. In alunite the maximum concentration corresponded to Nd and Sm. In jarosite concentrations decreased from La to Lu, except that a positive Eu anomaly was preserved from the precursor. These REE concentration patterns are interpreted as due to crystallographic factors, controlled by the best fit of REE with charge 3+ in the 12-fold coordination site of K in jarosite and alunite. This site is larger in jarosite and fits La best, whereas the smaller site in alunite best fits Nd and Sm. Goethite REE signature is variable, perhaps due to two formation routes, (1) silicates ➔ goethite and (2) silicates ➔ jarosite ➔ goethite. Our interpretations of REE concentration in alunite, jarosite and goethite are novel and provide new routes to further develop REE as tracers of acid alteration processes. [Display omitted] • Eu anomaly was negative in altered volcanic rocks, positive in altered shales. • Kaolinite, formed at pH 5–7, inherited the REE pattern of precursor phyllosilicates. • Alunite (pH 3–5) and jarosite (pH < 3) had a modified REE pattern with LREE > > HREE. • REE signature in alunite and jarosite is controlled by the size of the K crystallographic site. • Goethite variable REE signature is caused by two formation routes, from silicates or from jarosite. [ABSTRACT FROM AUTHOR]

Interest in mineral-microbe interaction has grown enormously over recent decades, providing information in a puzzle-like manner which points towards an ever increasingly intimate relationship between the two; a relationship that can be truly termed co-evolution. Clay minerals play a very central role in this co-evolving system. Some 20 years ago, clay scientists looked at clay mineral-microbe studies as a peripheral interest only. Now, can clay scientists think that they understand the formation of clay minerals throughout geological history if they do not include life in their models? The answer is probably no, but we do not yet know the relative weight of biological and inorganic factors involved in driving clay-mineral formation and transformation. Similarly, microbiologists are missing out important information if they do not investigate the influence and modifications that minerals, particularly clay minerals, have on microbial activity and evolution. This review attempts to describe the several points relating clay minerals and microorganisms that have been discovered so far. The information obtained is still very incomplete and many opportunities exist for clay scientists to help to write the real history of the biosphere. [ABSTRACT FROM AUTHOR]

Most known clay mineral reactions are slow. Clay formation by weathering is recognized as faster (hundreds of thousands to few million years) than clay reverse weathering (few to tens My), even if the latter takes place in deep diagenetic conditions at temperatures above 100 °C. Identifying hot spots of fast clay retrograde reactions acting as effective potassium sinks would contribute to eliminating the present imbalance of the potassium budget towards release into the oceans. We have identified and modeled the reaction kaolinite + Fe + cations → Fe - illite occurring in Brazilian mangroves, which takes place through kaolinite-smectite and illite-smectite intermediates. The reaction is very fast, transforming 72–154 g m − 2 y − 1 of kaolinite into Fe-illite, or 16–38% of the newly sedimented kaolinite each year. This kaolinite-to-illite transformation is 10s–100s times faster than kaolinite formation by weathering. Extrapolation of the calculated potassium consumption to mangrove forests worldwide produces 0.6–3 × 10 12 g y − 1 , or 1–6% of the yearly potassium riverine input into the oceans. [ABSTRACT FROM AUTHOR]

Fungi dissolve soil minerals by acidification and mechanical disruption. Dissolution may occur at the microscale (contact between fungus and mineral) and medium scale (entire mineral grains). Mineral weathering by fungi and other microorganisms is thought to be of significant global contribution, perhaps producing specific weathering signatures. We report fungal dissolution of phlogopite mica in experiments with three fungal strains ( Alternaria tenuissima, Cladosporium cladosporioides , Stilbella sp.) on solid medium for 30 days at 21 °C and 96–100% relative humidity. The study used variable-pressure SEM-EDS equipped with charge contrast imaging. Statistical analysis of the results discriminated between the weathering activities of the three fungal species, which increased from Stilbella sp. to C. cladosporioides to A. tenuissima , in agreement with the respective decreasing pH in the media (6.4, 5.8, 5.2 ± 0.03). Phlogopite weathering features were irregular and variable, apparently not caused by direct contact with fungal hyphae. EDS values indicated two or more dissolution mechanisms, one of them suggesting cation rearrangement in the mica towards formation of Al-rich smectite. Intimate fungus-mineral interaction was observed, and the lack of observable dissolution traces from such contact interaction is interpreted as the result of effacing by the more intense acid leaching operating at larger scale. [ABSTRACT FROM AUTHOR]

Land colonization by plants and their fungal and bacterial symbionts during the Paleozoic was fundamental to the evolution of terrestrial ecosystems, but how these early communities influenced mineral weathering and soil development remains largely unknown. We investigated cryptogamic ground covers (CGCs) in Iceland to identify modern analogous communities and to characterize soil structure and biologically mediated weathering features. Using a novel application of X-ray microcomputed tomography, we show that moss-dominated CGCs and their soils are not adequate analogues of early communities. Comparisons with the 407 Ma Rhynie Chert (Scotland) biota indicate that modern CGCs dominated by lichens, liverworts, and their associated symbionts (fungi, cyanobacteria) are more representative of early soil-forming communities. Liverwort and lichen soils are thin, and their depth and complexity are constrained by the size and growth form of the dominant plants or lichens. They are aggregated and stabilized by cyanobacteria, mycorrhizal and lichenized fungi, rhizoids, and associated exudates. Smectite was associated with liverwort but not with moss CGC soils. Soil grain dissolution features are diverse and attributable to different organisms (e.g., bacteria, fungi) and types of interaction (e.g., symbiosis). We postulate that such features provide a novel indirect means of inferring biotic interactions in paleosols. [ABSTRACT FROM AUTHOR]

The aim of this study was to further our understanding of the pedogenic and lacustrine modification of clay minerals. Some of these modifications are of special interest because they constitute reverse weathering reactions, rare in surface environments, and because there is not yet an accurate assessment of their global relevance in mineralogical and geochemical cycles. For this study, two sections from the Central System in Spain were selected. Both are sections through the Uppper Cenomanian-Turonian mixed clastic and carbonate succession, containing both calcite and dolomite, in the Sierra de Guadarrama. Mid-Turonian sea level fall resulted in the formation of a coastal plain environment in which extensive pedogenesis occurred around saline lagoons. The mineralogical changes that have occurred as a result of sedimentation in saline lagoons and as a consequence of pedogenesis are described. Textural relationships indicate that the dolomite cement pre-dates the calcite. Silicate minerals are represented by quartz, kaolinite, illite-smectite, illite, minor plagioclase and alkali feldspar, and trace chlorite and palygorskite. There is a positive correlation between the intensity of pedogenesis and the proportion of illite in the clay assemblage in one of the sections, indicating pedogenic illitisation. In this section, the intensity of the illitisation process increases up, reaching a maximum where pedogenesis is most intense in the middle part, and then decreases as marine influence increases towards the top of the Alcorlo Formation and the overlying marine Tranquera Formation. The clay assemblages are consistent with a slow transformation process from kaolinite to illite by way of illite-smectite, taking place under surface conditions. The illitisation process has resulted in a less Fe-rich, more Mg-, and Al-rich illite than the majority of previously documented cases in the near surface. Formation of Al-rich illite is not therefore restricted to the deep subsurface. The mechanism for low temperature illitisation involves enhanced layer charge resulting from Mg 2 + substitution for Al 3 + (or Fe 3 + ) and Fe 3 + to Fe 2 + reduction. Mg 2 + enrichment may have occurred principally in saline lagoons or lakes, while Fe 3 + to Fe 2 + reduction occurred as a result of wetting and drying in a pedogenic environment. So far as it has been possible to establish, this dual mechanism has not previously been documented. This study indicates clearly that the dolomite and calcite are authigenic cements that precipitated in a clastic sediment, probably soon after deposition. Dolomitisation and Mg enrichment of the clay may have occurred at the same time. Seawater is the most probable source of Mg. [ABSTRACT FROM AUTHOR]

Microbial activity following invasion of human-made structures and artifacts can have profound social and economic consequences including the permanent loss of cultural heritage. The unique frescoes in the 11th century Saint Sophia's Cathedral (Kyiv, Ukraine) have recently suffered from dark-spot biodeterioration. The aim of this work was to elucidate the microbial nature of biodeterioration and the biogeochemical processes occurring in the areas of the dark spots. Culture-independent approaches including scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), micro-X-ray diffraction and real-time quantitative polymerase chain reaction (qPCR) analysis were used in this study. SEM and qPCR data demonstrated that the main agents of fresco biodeterioration were mycelial fungi, with bacteria unlikely to play a major role in the development of the dark spots. SEM-EDS results showed that fungi colonization of the dark spotted areas resulted in mechanical and chemical weathering involving dissolution of mineral components of the plaster (mainly calcite) and displacement of mineral grains, which compromise the stability of the plaster or fresco. SEM-EDS also detected fungal biomineralization of secondary mycogenic minerals: calcium malate, hydrated aluminium and ferric phosphates. Biomineralization of calcium malate by fungi, as found in this study, is a rare biogeochemical phenomenon, possibly linked to the presence of calcite and nitrogen limitation. • 11th century frescoes in Saint Sophia's Cathedral (Kyiv, Ukraine) were affected by dark spot biodeterioration. • The main agents causing fresco defacement were filamentous fungi. • Fungi acted on fresco plaster through biomechanical and biochemical mechanisms. • Fungal activity resulted in dissolution of mineral components of the plaster, e.g. calcite. • Calcium malate, hydrated aluminum and ferric phosphate minerals were formed by fungi. [ABSTRACT FROM AUTHOR]

On Earth, trioctahedral (Mg-rich) vermiculite occurs as a transient alteration product of Mg/Fe2+-mica and chlorite, pyroxene, olivine, amphibole and even plagioclase where there is a nearby Mg source, indicating mild/short-lived weathering or hydrothermal conditions. On Mars, the abundant mafic rocks and low water availability suggest the likelihood of widespread vermiculite formation from the Noachian to the early Hesperian. Although it can be challenging to identify vermiculite by remote sensing or in situ infrared spectroscopy alone, we show that numerous previous remote sensing results suggest that vermiculite is widespread on the martian surface and perhaps a more common mineral on that planet than on Earth. Investigation of rocks from Riotinto (SW Spain) provides an example of how chlorite alters to vermiculite in an acidic environment. Similar incomplete vermiculite replacements of Mg/Fe2+-mica, chlorite and mafic minerals could have resulted on Mars from acidic to neutral weathering at low water regimes. While possible bias exists towards remote sensing detection of vermiculite on Mars in sites (1) with advanced alteration and (2) where vermiculite is not mixed (at pixel level) with other phyllosilicates, we find that vermiculite occurs in Noachian terrains, in sites (wider than pixel level) where other phyllosilicates are detected, and that vermiculite has more Fe3+ than is typical on Earth. [Display omitted] • Vermiculite is a transient alteration product of mafic minerals, mica and chlorite. • Vermiculite is widespread on Mars and found in Noachian altered terrains. • The mineral might be more commonplace on Mars than on Earth. • Most identified vermiculite on Mars so far is Fe3+-rich. • Existing biases suggest more occurrences and wider composition range. [ABSTRACT FROM AUTHOR]

A 3-m deep soil profile from Gran Canaria, Canary Islands, has been studied. The profile is interesting because soil development on mafic tephra produced a pattern of clay mineral and carbonate distribution. Carbonates precipitated abundantly, increasingly towards the bottom, making up 20–90 wt.% of the soil. Sepiolite and calcite are dominant at the top, whereas palygorskite and dolomite are the major components at the lower part of the profile. Quartz is present in low amounts in most of the profile, and smectite and non-crystalline partially altered tephra occur in low amounts towards the bottom. Mineralogical, chemical and textural investigations indicate that sepiolite and calcite precipitated in the space between the original tephra grains, from Ca, Mg and Si dissolved in situ and transported in the runoff. Palygorskite and smectite precipitated within tephra grains, from in situ tephra weathering, as well as dolomite. The distribution of the clay minerals is due to clay composition and ion mobility. Sepiolite, consisting only of Si and Mg, precipitated outside tephra grains, where the mobile Si and Mg ions were abundant in the interstitial waters. Palygorskite and smectite contain Si, Al, Fe, and Mg and only precipitated within the tephra grains, where the immobile Al and Fe were available. Calcite precipitation in solution is kinetically favored over that of dolomite and thus calcite precipitated between the grains. Dolomite precipitated within altering tephra grains and spherical clay structures because tephra and clay generated a viscous medium where dolomite supersaturation increased and the kinetic barrier for precipitation was overcome. These results are relevant to the “dolomite problem”, as they illustrate how dolomite can precipitate in surface conditions, and to CO 2 sequestration, because dolomite can immobilize higher CO 2 amounts (both Ca and Mg are involved and not only Ca) and in a much more stable manner (dolomite is eight orders of magnitude less soluble than calcite). [ABSTRACT FROM AUTHOR]

With the arrival of Curiosity on Mars, the MSL has started its ground validation of some of the phyllosilicate characterization carried out with remote sensing near-IR spectroscopy from orbital instruments. However, given the limited range of action of the rover, phyllosilicate identification and characterization will have to rely mainly on orbital near-IR data. Investigation of Earth analogs can greatly assist interpretation of martian spectra and enable more robust analyses. In this contribution, Mg/Fe-rich clays from submarine hydrothermal origin that had been thoroughly characterized previously were investigated with near-IR reflectance spectroscopy. The clays are mixed-layer glauconite-nontronite, talc-nontronite, talc-saponite, and nontronite samples. The hydroxyl bands in the range 2.1-2.35 μm were decomposed into their several individual components to investigate correlations between the octahedral chemistry of the samples and the normalized intensity of several bands. Good correlations were found for the samples of exclusive dioctahedral character (glauconite-nontronite and nontronite), whereas poor or no correlations emerged for the samples with one (talc-nontronite) or two (talc-saponite) trioctahedral layer components, indicating a more complex spectral response. Because these bands analyzed are a combination of the fundamental OH stretching and OH bending vibrations, the response of these fundamental bands to octahedral chemistry was considered. For 2:1 dioctahedral phyllosilicates, Fe and Mg substitution for Al displaces both fundamental bands to lower wavenumbers (longer wavelengths), so that their effect on the position of the combination band is coherent. In contrast, for trioctahedral clays, Al and Fe3+ substitution of octahedral Mg displaces the OH stretching band to lower wavenumber values, and the OH bending band to higher wavenumber values, resulting in partial or total mutual cancelation of their effects. As a result, clays with near-IR spectra indicating Mg-dominated octahedral compositions may in fact contain abundant Fe and some Al substitution. Thus, remote-sensing near-IR mineralogical and chemical identification of clays on Mars appears relatively straightforward for dioctahedral clay minerals but more problematic for trioctahedral clays, for which it may require a more detailed investigation of their near-IR spectra. [ABSTRACT FROM AUTHOR]

Saharan dust can travel long distances in different directions across the Atlantic and Europe, sometimes in episodes of high dust concentration. In recent years it has been discovered that Saharan dust aerosols can aggregate into large, approximately spherical particles of up to 100 μm generated within raindrops that then evaporate, so that the aggregate deposition takes place most times in dry conditions. These aerosol aggregates are an interesting phenomenon resulting from the interaction of mineral aerosols and atmospheric conditions. They have been termed “iberulites” due to their discovery and description from aerosol deposits in the Iberian Peninsula. Here, these aggregates are further investigated, in particular the role of the clay minerals in the aggregation process of aerosol particles. Iberulites, and common aerosol particles for reference, were studied from the following periods or single dust events and locations: June 1998 in Tenerife, Canary Islands; June 2001 to August 2002, Granada, Spain; 13–20 August 2012, Granada; and 1–6 June 2014, Granada. Their mineralogy, chemistry and texture were analysed using X-ray diffraction, electron microprobe analysis, SEM and TEM. The mineral composition and structure of the iberulites consists of quartz, carbonate and feldspar grains surrounded by a matrix of clay minerals (illite, smectite and kaolinite) that also surrounds the entire aggregate. Minor phases, also distributed homogenously within the iberulites, are sulfates and Fe oxides. Clays are apparently more abundant in the iberulites than in the total aerosol deposit, suggesting that iberulite formation concentrates clays. Details of the structure and composition of iberulites differ from descriptions of previous samples, which indicates dependence on dust sources and atmospheric conditions, possibly including anthropic activity. Iberulites are formed by coalescence of aerosol mineral particles captured by precursor water droplets. The concentration of clays in the iberulites is suggested to be the result of higher efficiency for clay capture than for the capture of larger mineral grains. The high hygroscopicity of clay minerals probably causes retention of water in the evaporation stage and some secondary minerals (mainly gypsum) are associated with clays. [ABSTRACT FROM AUTHOR]

Soil formation occurs through numerous physical and chemical weathering processes acting to alter the parent rock on the Earth's surface. Samples of surface soils were collected over a range of elevations (2000-3600 m) from profiles directly overlying basaltic to more felsic parent rocks, over a region in NW Ethiopia. The soils were investigated to determine their chemical composition and X-ray diffraction was used to identify and quantify individual mineral phases. The data set was analyzed using non-parametric statistics (Spearman's Rank and Mann-Whitney U tests) to compare the soils forming over the two parent rocks. Principal component analysis (PCA) was used to identify the mineral alteration assemblage and formation during pedogenesis. The extent of alteration was quantified using several chemical weathering indices (Chemical Index of Alteration = CIA; Chemical Index of Weathering = CIW), including an index calculated by multivariate analyses of the soil chemical composition data (weathering "W" index). Further to this we devised and tested a new weathering index (Wmin) using multivariate analysis of the soil mineralogy, to estimate the extent of weathering and physico-chemical proprieties of the parent rock from which the soil formed. The soils present a fair to advanced stage of alteration, with abundant iron (Fe) oxides (up to 40 wt%) and phyllosilicates (up to 57 wt%), including kaolinite-smectite (K-S) mixed-layer phases. The K-S was composed of either 30-50% kaolinite or 94-98% kaolinite layers. Discrete kaolinite was also present. The bimodal K-S mineralogical composition is likely due to two precursor phases: feldspar for the kaolinite-rich K-S and volcanic glass for the smectite-rich K-S. K-S with intermediate composition (50-94% kaolinite) was rare, due to its instability. Statistical analysis showed significant differences between the chemical compositions of the soils developed on the two different parent volcanic compositions. The soils overlying the more felsic parent rocks were less altered than those overlying the flood basalt. When comparing the weathering indices calculated in this study, we conclude that while the CIA and CIW may be more readily determined, the W and Wmin indices can elucidate information on the composition of the original rock from which they formed. The W index is more sensitive to certain variables when compared with the newly derived mineralogical Wmin index; however the Wmin index takes into account mineral phases within the sample, which provides a more detailed interpretation of weathering rates than chemistry alone. In addition the Wmin index correlated with meteorological variables, such as elevation (and consequently temperature and precipitation), known to influence the degree of pedogenesis. The Wmin index can be used to enhance our understanding of the processes that occur during weathering processes to supplement information gained from traditional chemical weathering indices. [ABSTRACT FROM AUTHOR]

Near-infrared remote sensing data of Mars have revealed thousands of ancient deposits of Fe/Mg-rich smectitic clay minerals within the crust with relevance to past habitability. Diagnostic metal–OH infrared spectroscopic absorptions used to interpret the mineralogy of these phyllosilicates occur at wavelengths of 2.27–2.32 μm, indicating variable Fe/Mg ratios in the clay structures. The objective of this work is to use these near infrared absorptions to constrain the mineralogy of smectites on Mars. Using Fe/Mg-rich seafloor clay minerals as mineralogical and spectroscopic analogs for Martian clay minerals, we show how crystal–chemical substitution and mixed layering affect the position of the diagnostic metal–OH spectral feature in smectitic clay minerals. Crystal-chemistry of smectites detected on Mars were quantitatively constrained with infrared data and categorized into four mineralogical groups. Possible alteration processes are constrained by comparisons of clay chemistry detected by remote sensing techniques to the chemistry of candidate protoliths. Of the four groups identified, three of them indicate significant segregation of Fe from Mg, suggestive of alteration under water-rich and/or oxidizing conditions on Mars. The fourth group (with low Fe/Mg ratios) may result from alteration in reducing or water-limited conditions, potentially in subsurface environments. Some samples are interstratified di–trioctahedral clay minerals that have characteristics of dioctahedral clay minerals but clear chemical evidence for trioctahedral sheets. Approximately 70% of smectite deposits previously detected on Mars are classified as Fe-rich (FeO/MgO > 10). Only 22% of detections are trioctahedral and relatively Mg-rich. An additional ∼8% are difficult to characterize, but might be very Fe-rich. The segregation of Fe from Mg in Martian clay minerals suggests that Mg should be enriched in other contemporaneous deposits such as chlorides and carbonates. [ABSTRACT FROM AUTHOR]

• Kaolinite transforms into Fe-smectite and Fe-illite in mangrove soils. • REE were not influenced by anthropic activity. • There is a trend of depletion of Heavy REE (HREE)in the normalized patterns. • Terrigenous kaolinite control the fractionation of light REE (LREE) over HREE. • Adsorption of HREE by 2:1 clays reduced the fractionation of LREE over HREE. Mangroves are intertidal tropical ecosystems influenced by marine and terrigenous input. They are important sinks of trace elements, like Rare Earth Elements (REE), which are recognized as excellent indicators of geochemical processes in estuaries. REE data of bulk soil samples from eight mangroves located along the Brazilian coast were correlated with quantitative clay mineral data based on XRD full-profile modelling. Kaolinite has been found to transform to Fe-illite in these mangroves. The clay assemblage was dominated by interstratified phases, including kaolinite-smectite (kaolinite and smectite-rich), illite–smectite and other illitic phases. REE concentrations in bulk soils were LREE > MREE > HREE (where L, M and H indicate light, medium and heavy). Multivariate statistical approach (PCA analysis) using clay mineral concentrations and proxies for relative REE concentrations ([La/Gd] N , [La/Yb] N and [Gd/Yb] N ratios) showed (r > 0.75) that fractionation of LREE over HREE was highest in mangroves where kaolinite, fed with the highly weathered sediments form the Neogene Barreiras Group, was most abundant (67–85% of all clay minerals), while REE fractionation decreased as the relative proportion of Fe-rich smectite increased (26–46 % of all clay minerals). Identified processes of REE control are: 1) Level of sediment weathering within the continent, where higher weathering implies higher kaolinite content and higher REE fractionation (LREE > MREE > HREE); 2) selective leaching of LREE from mangrove soils by saline water; 3) preferential adsorption of HREE by Fe-rich smectite and illite neoformed in the mangrove soils. It is possible to conclude that clay minerals exert an important control on REE fractionation in tropical mangroves. [ABSTRACT FROM AUTHOR]

Abstract: Seafloor hydrothermal sites generate abundant Mg- and Fe-rich clays. These clays are structurally and compositionally interesting because these environments are characterized by large, dynamic temperature and chemical gradients in their deposition environment, which promote the formation of chemically and structurally complex clays, including interstratified phases. The system is also interesting as a proxy for the study of the large Mg- and Fe-rich phyllosilicate deposits on Mars, which are broadly characterized as smectitic clay of hydrothermal, volcanic or sedimentary origin. Thirty submarine samples and four terrestrial ones, for comparison, were studied by means of X-ray diffraction (XRD), thermogravimetry (TG), mid-IR and Mössbauer spectroscopies and chemical analysis. The samples include nontronite and the mixed-layer phases glauconite–nontronite, talc–nontronite and talc–saponite. Some of the talc–saponite samples have Fe contents well above those typical for these Mg-rich, trioctahedral phases (up to 1.69 Fe per O10[OH]2, in the tetrahedral and octahedral sheets). Tetrahedral Fe ranges from 0 to 0.66atoms per O10[OH]2 across the samples. As found in previous studies of similar specimens, Fe promotes the retention of molecular water that is released upon heating above 200C, and is mainly emplaced in non-expandable layers (talc and glauconite layers). In talc–nontronite and talc–saponite octahedral Fe (both di- and trivalent) appears to be bound to this trapped molecular water, whereas in glauconite–nontronite the bond appears to be with tetrahedral Fe. Samples typically show more than one dehydroxylation event in the TG analysis. The weight loss at each dehydroxylation event is broadly consistent with the proportion of individual layers as determined by means of XRD, but there is no good correlation between both. By contrast, the weight loss at each dehydroxylation event correlates with the chemistry of the layers, where certain cations promote chemical domains in the octahedral sheet (e.g., trioctahedral, nontronite-like, and montmorillonite-like) that dehydroxylate at the several temperatures. The correlations found for talc–nontronite and glauconite–nontronite samples suggest that the distribution of cations in the octahedral sheets of most, but not all, samples is intermediate between total dispersion and total segregation, perhaps random. The talc–nontronite samples have talc layers with cation-deficient octahedral sheets. The above results are best explained by layers of polar character, where the octahedral sheets are composed of domains with different chemical characteristics corresponding to the two types of layers in the interstratified clay. The existence of molecular water (bands at 1635 and 3300–3500cm−1, or ~6.1 and 2.9–3.1μm, respectively) bound in non-expanding layers is relevant to the mineral characterization of Martian Fe-rich clays with spectroscopic methods, where molecular water is so far assumed to be linked to smectite. The variety of mixed-layer clays in which Fe is found in the submarine samples suggests that mixed-layering may be important in Martian clays, which are spectroscopically variable but generally Fe-rich. [Copyright &y& Elsevier]

Abstract: The effect of oil on As(V) adsorption on clay minerals has been investigated using batch experiments at low and high pH, NaCl concentration and oil contents. Four clay minerals were chosen because of their abundance in sediments and their different crystal chemistry: illite, kaolinite, montmorillonite, and chlorite. The values for pH were 4 and 8 and salt concentrations were 0.001 and 0.7M NaCl to appreciate the effects of changing salinity, e.g. from fresh water to seawater conditions. For the coating experiments, a well-characterised oil was used to survey the main effects of complex organic mixtures on adsorption and oil to clay mineral (w/w) ratios were 0.0325 and 0.3250. As(V) adsorption increased with increasing NaCl concentration, suggesting that the mechanisms of As(V) adsorption are related to the formation of surface complexes in which Na+ ions act as bridges between the clay surface and the As(V) anions. Cation bridging is also indicated by zeta potential measurements which show that higher NaCl concentrations along with the presence of As(V) can cause the clay particles and adsorbed ions to have a more negative overall charge. Adsorption is lower at higher pH due to the reduced number of positively charged sites on the edge of clay mineral layers. Oil coating reduces As(V) adsorption by decreasing the available surface area of clay minerals, except in the case of oil-coated montmorillonite, where surface area following dispersion in water is increased. The main variables controlling As(V) adsorption are surface area and surface charge density, as confirmed by a simplified quantitative model. These findings advance our ability to predict the effects of complex pollution events in various freshwater and marine settings. [Copyright &y& Elsevier]

The cameras on the Pathfinder probe (Imager for Pathfinder) and the rovers Spirit and Opportunity (Panoramic Camera), Curiosity (Mast Camera) and Perseverance (Mast Camera-Z) produce visible-range spectra of limited wavelength resolution but of great target resolution which allows mineralogical analysis of selected areas within martian rocks. Laboratory spectra of relevant specimens were transformed into the spectra corresponding to each of the above cameras to increase our capability to interpret martian spectral data collected in-situ. The focus was on finding spectral features that can be detected by the cameras on Mars and are diagnostic of specific minerals. The samples are a collection of (1) Fe/Mg-phyllosilicates from submarine hydrothermal sites and (2) of rocks from acid alteration environments containing goethite, hematite, jarosite and Fe-bearing chlorite as these minerals are detectable in the extended visible range. Among all the samples, interstratified glauconite-nontronite has the most unique spectral features and should be easily detectable with the rover cameras. The spectral features of talc from Fe-bearing interstratified specimens are described. These data are especially relevant as glauconite and talc have been proposed to be fairly abundant on Mars and their detections are suggested from remote-sensing near-IR data. Several indices are proposed to assess Fe content on the investigated samples as well as mineral concentration of goethite and hematite. Among these indices, the normalized spectral slope in the range 420–600 nm increases with total Fe content for all samples, whether phyllosilicates, oxides or sulphates (R2 = 0.7–0.8). For pure phyllosilicates, the slope from 600 to 1010 nm decreases with increasing octahedral Fe (R2 = 0.75). An index for goethite produced excellent results assessing goethite concentration (R2 = 0.84). Of all cameras, Mast Camera reproduces the spectra with lowest fidelity and generates the poorest correlations between indices and tested variables. The other three cameras perform similarly. [Display omitted] • Lab spectra of Earth analogues shown with the resolution of martian rover cameras. • Spectral fidelity of Fe-clays and Fe oxides is: IMP, PanCam, MastCam-Z > MastCam. • Interstratified glauconite-nontronite easily recognizable on Mars by rover cameras. • Spectral features of Fe-rich talc and interstratified talc layers are shown. • Spectral indexes correlate well with Fe content and goethite content in samples. [ABSTRACT FROM AUTHOR]

Biological activity plays a substantial role in the geochemistry of the Earth's surface. Particularly interesting are effects on clay formation because clays are abundant and have high surface-to-volume ratio, resulting in clays making up a large fraction of the overall mineral-fluid interface and having an effective control of mineral reactions. Thus, biological control on clay composition would affect element budget globally and the mineralogy of subsequent diagenetic processes. Biological acceleration of clay production would result in enhanced clay control of mineral reactions and faster organic C sequestration, by adsorption on clay minerals, with implications for the C and related cycles. We investigated the combined effect of microbial activity and water chemistry on the composition of neoformed clay by reacting volcanic glass with natural waters covering a large composition range (fresh water from a lake and a spring, seawater, and hypersaline water). The microbes (bacteria, fungi, and algae) were totally or partially identified using molecular and microscopy techniques. The solid alteration products were analyzed using cryo-SEM to investigate the mineral-microbe interface and TEM-AEM to study the composition of the neoformed clay. The solution chemistry was also investigated. We found that clay composition was controlled mainly by glass chemistry, rather than biological activity, through a mechanism of in situ transformation. The resulting clay was Al-rich (dioctahedral composition). In one case (inorganic experiment, freshwater lake), the specific inorganic conditions of pH and Mg and Si concentration promoted formation of Mg-rich (trioctahedral clay). Microbes, however, did influence clay composition by confining glass grains in biofilms where water chemistry is significantly different from the bulk solution. Alteration in such conditions generated significant amounts of trioctahedral, Mg-rich clay in the hypersaline water experiment, whereas it favored production of dioctahedral, Al-rich clay in the freshwater lake experiment. It is thus demonstrated that biofilms can exert an effective control on clay mineralogy. [ABSTRACT FROM AUTHOR]

Abstract: Aluminous clay deposits on Mars are recognized from remotely sensed infrared spectral features similar to those of montmorillonite, beidellite, and/or kaolinite. The nature of aluminous clay deposits on Mars is of interest because they likely indicate a different formation mechanism than that of Fe–Mg clays, which are widespread on Mars and likely alteration products of the Fe–Mg-rich basaltic crust. The near-infrared reflectance spectra of aluminous martian clay deposits frequently display characteristics typical of both montmorillonite and kaolinite. The question arises whether such mixed character is due to the existence of end-member phases or to kaolinite–smectite mixed-layer (K–S). The issue is relevant because K–S implies the existence of a smectite precursor that alters into kaolinite, and thus constrains the timing and intensity of the alteration processes that generates it. A mixture of kaolinite and smectite end-members may indicate locally heterogeneous alteration processes, or alternatively, could result from the physical mixing of altered materials of different provenance. A group of natural K–S samples and synthetic kaolinite/smectite mixtures of known proportion, all of which had been thoroughly characterized in previous work using several analytical techniques, were investigated here using near-infrared (NIR) spectroscopy. The NIR spectral features correlate well with their kaolinite–smectite relative proportions. The shape of spectral features attributed to Al–OH in K–S is subtly different from those in physical mixtures of kaolinite and smectite. Based on qualitative comparison, some regions on Mars appear to have spectral signatures similar to K–S. We also applied a quantitative technique using the second derivative of spectra. In this technique, plots of the height of the features at (λ=) 2.21μm (band present in kaolinite and montmorillonite) and 2.17μm (kaolinite only) were able to discriminate between K–S and kaolinite–smectite physical mixtures, as they generated correlations with different slopes. The method of discrimination was applied to Mars spectra, which resulted in reasonable evidence for the existence of K–S in Nili Fossae and Mawrth Vallis, and mixtures of end-members in Mawrth Vallis and Leighton Crater. This is one of the first times that evidence for mixed-layer clay minerals, and particularly K–S, on Mars has been gathered. The ability to detect mixed-layer clays is an important step forward for further development of our understanding of the processes that generated clay on Mars. [Copyright &y& Elsevier]

Abstract: Six-year experiments of volcanic glass reacting with waters of different chemistry (two freshwaters, seawater and brine) at ∼22°C have produced the thorough transformation of mm-size glass chips into quartz, with minor alunite and calcite. These results contradict the current thinking about glass weathering and quartz formation. The reaction from glass to quartz took place at an estimated velocity ranging from 300–2000 times to 106 times faster than the accepted values for quartz precipitation, depending on how rates were assessed. The most likely process taking place is the rapid transformation of cation-depleted glass into quartz. In addition, alunite formed very efficiently from low-S glass (40±15ppm). Such effective reaction in the absence of the accepted conditions for alunite formation is attributed to the high Al and K content combined with the generation of low pH conditions at the microscale. Local, low-pH conditions may arise due to proton-for-Na substitution at the earliest stage followed by liberation of the protons as glass later corroded. The surprising results show a new pathway of glass weathering and point towards reactions controlled by microscale conditions producing high activities locally. Such conditions may be common in the mineral–fluid interface with saline waters, immobile waters or systems with low water:rock ratios. The rapid precipitation of quartz at low temperature is relevant to the origin of quartz and the silica budget in a variety of sedimentary environments and prompts their reconsideration. [Copyright &y& Elsevier]

Abstract: The legendary cruise of H.M.S. Challenger (1872–1876) around the globe must always occupy an eminent place in the annals of oceanography, as being the first systematic attempt made on a global scale to explore the ocean. This expedition made fundamental discoveries in biology and geology which have not been surpassed by any later scientific cruise. Sediment with high content of metals (later called “metalliferous”) was among the enigmatic findings taken onboard. Although the nature of metalliferous sediments is well known today, the very first sampled sediments of this type have not been studied to date. Motivated by the historical value of Challenger’s metalliferous sediment collection we undertook an investigation addressing two questions: (1) the composition of sediments from seafloor for which we have very limited data; (2) Sr–Nd–Pb–Fe–Zn-isotope signature of these sediments collected before the substantial human impact on the ocean during the 20th century. The SE Pacific metalliferous sediments sampled by the Challenger’s explorers are of 2 types: (1) metalliferous oozes blanketing ridge crests and flanks down to the calcite compensation depth (CCD); and (2) stripped of CaCO3 metalliferous sediments located beneath the CCD in the deeps near the mid-ocean ridges. The abiogenic part of these sediments is composed mainly of poorly-crystalline to X-ray amorphous Fe–Mn-oxyhydroxides, and an amorphous silicate phase. These sediments have geochemical features similar to those of all the other metalliferous sediments: very high Fe and Mn content (on abiogenic basis), very low Al/(Al+Fe+Mn), and high content (on abiogenic basis) of As, Ba, Be, Bi, Cd, Co, Cu, Mo, Ni, Pb, Sb, Th, Tl, U, V, W, Y, Zn and Zr. Their REE distribution patterns are similar to that of deep seawater and show weak signs of hydrothermal imprint (weak positive or no Eu anomaly). Seawater and/or terrigenous input from South America control the Sr–Nd–Pb-isotope signature of the Challenger metalliferous sediments and have almost completely obliterated any original MORB-derived hydrothermal signal. Zn isotopes are mainly contributed from seawater although other Zn sources (hydrothermal fluid and detrital aluminosilicates, barite and volcanic glass) are necessary to fully explain Zn-isotope ratios. Fe isotopes indicate relatively slow Fe2+ to Fe3+ oxidation in the non-buoyant plume, thus producing relatively lighter Fe-isotope signature of the FeOOH particles that formed the studied metalliferous sediments. [Copyright &y& Elsevier]

The extent of natural weathering of phiogopite crystals in a karstic environment and the composition of its weathering products have been examined through a multi-method investigation carried out on a volcanoclastic deposit discovered in the Grotta del Cervo cave, Pietrasecca, central Italy. Phlogopite crystals are a mixture of 1M and 2M1 polytypes and show mixed- layering with a low amount (1-4%) of smectite in the glass groundmass. Phiogopite crystals vary in composition from phlogopite to ferroan phiogopite. Their average structural formula is (K0.92Na0.03Ba0.03Ca0.02) (Mg2.05Al0.01Fe2+0.19Fe3+0.04Mn0.01Ti0.15 0.19 (Si2.63Al1.37)O10.16(OH1.57F0.27). Micromorphological, X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), scanning electron microscopy (SEM), and microprobe analyses (EMPA) showed that the mineralogical evolution of phiogopite crystals is consistent with in-situ pseudomor- phic weathering of mica to Al-rich dlioctahedral (rather than Mg-rich) clay minerals (beideffite-like) via phlogopite-smectite mixed-layer phases. The main mechanism of transformation is a layer-by-layer modification in which water composition, enriched in Si and Al from glass dissolution, is a major control. Mg loss, Ca and Na exchange for K, enrichment in Si and Al are the main processes required for beidellitization of phiogopite. Glass alteration produced sequentially smectite, chabazite, phillipsite and analcime, as leaching progressed and the interstitial fluids became increasingly alkaline. The type of zeolite found in the several samples (in the chabazite, phillipsite, analcime series) indicates that the alteration extent increases from wall to the ceiling and to the floor of the cave. [ABSTRACT FROM AUTHOR]

Abstract: Amino acid–smectite interaction may have catalyzed prebiotic reactions essential for the emergence of life. Lysine solutions (0.05 M) were reacted with Na-smectite in adsorption–desorption experiments. The lysine–smectite complexes were heated at 80 °C for 10 days to investigate (1) possible slow processes taking place at surface temperature that would be accelerated at higher temperature and (2) processes taking place in hydrothermal systems. Three sets of experiments were performed: thermal treatment in closed tubes and water added regularly; thermal treatment in closed tubes without adding water; and thermal treatment in open tubes and no added water. After lysine desorption (displacement with 0.1 M CaCl2), the solutions were investigated using circular dichroism (CD) and the smectite samples using FTIR and CHN elemental analysis. CD spectra were dependent on the solution pH, which was controlled by lysine protonation state. The lysine protonation state was altered by the adsorption–desorption process, with a higher Lys+/Lys± ratio after desorption. The CD and CHN analyses show that the thermal treatment in a moist state causes stronger smectite–lysine binding. FTIR data suggest that the stronger binding is caused by more or stronger H bonds between –NH+ 3 lysine groups and smectite basal O atoms. [Copyright &y& Elsevier]

The model of Fe3+ distribution between octahedra and tetrahedra in dioctahedral smectites by Decarreau and Petit (2014) used data from infrared analysis. From their own and other general evidence, the resulting data are likely to be affected by significant uncertainty. This aside, their model has limited application because it is based on synthetic smectites containing only Si, Al, and Fe3+. [ABSTRACT FROM AUTHOR]

Clay samples of hydrothermal origin from several oceanic spreading centers were studied using XRD, microprobe, infrared, and thermal analysis. They are talc, smectite, and mixed-layer talc-smectite (T-S) where the talc layers have several degrees of crystalline order. The smectite is trioctahedral in most cases, but there is also dioctahedral smectite both as mixed-layer and as a separate phase. All specimens contain Fe3+, some of them in moderate amounts (up to 17% Fe2O3) distributed between the tetrahedral and octahedral sheets (maximum values: IVFe = 0.32, VIFe = 0.68, per O10[OH]2). Octahedral Fe abundance correlates with the presence of molecular water that is lost in a well-defined dehydration event above 200 °C. This water does not cause layer expansion and is interpreted to be present within the pseudo-hexagonal cavity, next to Fe3+ ions that generate a local charge imbalance. The presence of octahedral Fe3+ is accompanied by vacancies in the octahedral sheet to balance the excess positive charge. An infrared band at ~790 cm-1 is assigned to OH bending in the group Fe-Mg-〉-OH. Analysis of this band suggests a range of short-range Fe-〉 distributions, from random to ordered. Our sequence talc, T-S, trioctahedral smectite is defined by an increasing Al for Si substitution in the tetrahedra and increasing crystal disorder. The presence of Fe also causes crystal defects. This mixed-layer series can be considered as a continuum generated by the combination of chemical and crystal defect variability. Kerolite was used to designate disordered, hydrated talc. We find that there is no clear line delimiting talc from kerolite as a single phase or in mixed-layer minerals and that it is better to use a descriptive term for the latter such as "disordered talc." Dioctahedral smectite is also a possible end-member of the mixed-layer sequence, which implies an Al + 〉 for Mg substitution in the octahedral sheet. If T-S consists of polar TOT layers, the existence of dioctahedral smectite in T-S raises the question of the actual composition of the octahedral sheets within polar TOT layers. [ABSTRACT FROM AUTHOR]

Nuclear waste from thermal plants poses a lasting risk to the biosphere because of its long radioactive life. The planned definitive storage place for it is in deeply buried repositories. Such repositories would need to be both impermeable to water, and plastic during deformation, in order to avoid the formation of cracks that may allow water in. One of the clay minerals, smectite, has these two properties and is an ideal candidate as a sealing material or even host rock for nuclear waste repositories. The chemical stability of smectite in the repository environment is sufficient to maintain good sealing properties during the active life of the relevant radionuclides. [ABSTRACT FROM AUTHOR]

Abstract: Talc, kerolite–smectite, smectite, chlorite–smectite and chlorite samples from sediments, chimneys and massive sulfides from six seafloor hydrothermal areas have been analyzed for mineralogy, chemistry and oxygen isotopes. Samples are from both peridotite- and basalt-hosted hydrothermal systems, and basaltic systems include sediment-free and sediment-covered sites. Mg-phyllosilicates at seafloor hydrothermal sites have previously been described as talc, stevensite or saponite. In contrast, new data show tri-octahedral Mg-phyllosilicates ranging from pure talc and Fe-rich talc, through kerolite-rich kerolite–smectite to smectite-rich kerolite–smectite and tri-octahedral smectite. The most common occurrence is mixed-layer kerolite–smectite, which shows an almost complete interstratification series with 5 to 85% smectitic layers. The smectite interstratified with kerolite is mostly tri-octahedral. The degree of crystal perfection of the clay sequence decreases generally from talc to kerolite–smectite with lower crystalline perfection as the proportion of smectite layers in kerolite–smectite increases. Our studies do not support any dependence of the precipitated minerals on the type/subtype of hydrothermal system. Oxygen isotope geothermometry demonstrates that talc and kerolite–smectite precipitated in chimneys, massive sulfide mounds, at the sediment surface and in open cracks in the sediment near seafloor are high-temperature (>250 °C) phases that are most probably the result of focused fluid discharge. The other end-member of this tri-octahedral Mg-phyllosilicate sequence, smectite, is a moderate-temperature (200–250 °C) phase forming deep within the sediment (∼0.8 m). Chlorite and chlorite–smectite, which constitute the alteration sediment matrix around the hydrothermal mounds, are lower-temperature (150–200 °C) phases produced by diffuse fluid discharge through the sediment around the hydrothermal conduits. In addition to temperature, other two controls on the precipitation of this sequence are the silica activity and Mg/Al ratio (i.e. the degree of mixing of seawater with hydrothermal fluid). Higher silica activity favors the formation of talc relative to tri-octahedral smectite. Vent structures and sedimentary cover preclude complete mixing of hydrothermal fluid and ambient seawater, resulting in lower Mg/Al ratios in the interior parts of the chimneys and deeper in the sediment which leads to the precipitation of phyllosilicates with lower Mg contents. Talc and kerolite–smectite have very low trace- and rare earth element contents. Some exhibit a negative or flat Eu anomaly, which suggests Eu depletion in the original hydrothermal fluid. Such Eu depletion could be caused by precipitation of anhydrite or barite (sinks for Eu2+) deeper in the system. REE abundances and distribution patterns indicate that chlorite and chlorite–smectite are hydrothermal alteration products of the background turbiditic sediment. [Copyright &y& Elsevier]

Abstract: Amino acid adsorption on smectite is relevant to prebiotic processes involving possible catalytic reactions in the early Solar System, as implied by the clay-organic correlation found in meteorites, and the generation and modification of organic components essential for the origin of life. Here we report the results of a study investigating the adsorption of l-lysine (0.025–0.4M) onto montmorillonite. The reaction products were studied using X-ray diffraction, chemical analysis and infrared spectroscopy. We find that lysine adsorption is first dominated by cation exchange and then by adsorption of electrically neutral lysine (as a zwitterion), as indicated by chemical and FTIR evidence. At the maximum concentration, lysine displaces only ∼1/3 of the original interlayer cations. The d-spacing of the smectite–lysine complex increases from 1.2 to 2.1nm as more lysine enters the interlayer space, and water is expelled. We propose a structural model of lysine sorption in the interlayer in which lysine is oriented at >45–90° to the plane of siloxane O atoms. [Copyright &y& Elsevier]

Abstract: The kinetics of smectite illitization in shale samples from eight wells have been modeled using the equation −dS/dt = kK 0.25 S 5 [Cuadros, J., Linares J., 1996. Experimental kinetic study of the smectite-to-illite transformation. Geochim. Cosmochim. Acta 60, 439–453], where S is the proportion of smectite layers in illite-smectite (I–S), t is time, k is the rate constant and K is the concentration of potassium. The I–S compositions and the physical parameters were obtained from the literature. Potassium concentration is the only unknown parameter and it was chosen to fit the experimental data. I propose that this variable is termed “effective K concentration,” as it is affected not by the actual K concentration alone but also by those of other cations that compete with K for the smectite interlayer sites, especially Ca, by ion mobility in the sediments and possibly by other variables. The kinetic equation allows an accurate fit to the experimental data in all the wells, reproducing both the illitization onset and the patterns of the plots of % smectite vs. depth. The relative changes of the values of “effective K concentration” compare well with K/Ca equivalent ratios in the whole rock. Three of the modeled wells, located in near proximity, produced similar “effective K concentration” patterns. These results support the validity of the equation used in the models. They also suggest that this equation can be used to assess K concentrations in sediments and K mobility within basins. [Copyright &y& Elsevier]

Investigates the formation of smectite under hydrothermal conditions in the aluminum-magnesium series. Types of smectite clays based on their charges; Models rationalizing kaolinite and smectite growth; Chemical analysis of gels; Difference in the growth rate of trioctahedral and dioctahedral smectite; Precursors to the growth of smectite.

Phlogopite flakes strewn on the soil of Caldara di Manziana (Italy) display multiple minute perforations. The site is a caldera linked to recent volcanism (90 ka to 0.8 Ma) with present emanations of CO2 (~150 t d−1) and H2S (~2.55 t d−1). Stereomicroscopy and SEM–EDX observation of the phlogopite crystals shows holes and depressions <200 µm to 2 mm across. They are circular, pseudo-hexagonal, or irregular. Within the depressions, there are deposits of phlogopite alteration products consistent with a sulphuric acid attack, showing loss of Mg and K. Some are thin and homogeneous; others are thick, irregular, and chemically heterogeneous, including plates, flakes, tubes of Fe-beidellite or Fe-bearing halloysite, silica, Fe oxides, and gypsum. Areas of phlogopite surface are also altered. Sulphuric acid is produced from the H2S gas by the mediation of sulphur-oxidizing bacteria. Pseudo-hexagonal perforations are interpreted to result from slow acid attack with dissolution controlled by phlogopite crystal symmetry. Some depressions developed surrounding films of pseudo-hexagonal shape, interpreted as jarosite crystallizing radially outwards from the depressions. This style of acid attack is possibly promoted by local high humidity and precipitation that generate long-lived water droplets and films on mineral surfaces where sulphuric acid is active for prolonged times. [ABSTRACT FROM AUTHOR]

Analyzes iron segregation in the octahedral sheet of bentonitic illite-smectite (I/S). Cation arrangement and order-disorder in minerals presenting isomorphous distributions; Existence of medium- or long-range ordering of cations in the octahedral sheets of the most illitic I/S samples.

Highlights a study which investigated the smectite-to-illite transformation mechanism through an analysis of mixed-layer illite-smectite from different locations in North America and Europe. Significance of this transformation mechanism; Details on the samples which were studied; Details on optical microscopy, scanning electron microscopy and X-ray diffraction of bulk rocks; Information on atomic force microscope analysis; Results of the study.

Reports on the performance of BET surface area measurements and XRD and TG analysis on a mixed-layer illite/smectite with 11 percent illite. Effects of the exchange cation on the surface area of clays; Information on the exchanged samples studied.

Iron electronic transitions produce intense colors in minerals with moderate to high Fe content, which phenomenon allows using color and visible spectroscopy to identify and quantify Fe-bearing minerals. This approach is especially useful for Mars investigation due to the limited analytical instruments available at Mars. The challenges are: (1) overlap between Fe electronic absorption bands of Fe-bearing minerals, (2) band wavelengths are modified by chemical and structural variables, and (3) particle size effects can modify mineral color. The magnitude of these difficulties, however, depends on the mineral mixture investigated. In this study, we further probe the potential of visible-range data for investigation of Fe-minerals. The samples were mineral mixtures from the Riotinto area (SW Spain) that resulted from acidic alteration and contained Fe in oxy-hydroxides, hydroxysulfates and phyllosilicates. Samples were studied using visible/near-infrared spectroscopy, X-ray diffraction and thermogravimetry. The wavelength range 320–1000 nm was investigated using spectral second derivatives and CIELAB color parameters. Hematite was readily detected, below X-ray diffraction detection limits, from the band at 520–560 nm. Jarosite was readily identified by the combined presence of bands at ~390 and ~ 440 nm. Thermogravimetric and CIELAB color analyses indicated goethite as the most common Fe-rich mineral in the samples. Correlations between CIELAB color parameters were controlled by goethite, where jarosite-rich specimens aligned with the correlations but some samples containing hematite plotted outside them. Quantification of goethite was attempted as calibrated against thermogravimetric data. Calibration was not possible below ~10 wt% goethite. Above this value, results from spectral second derivatives allowed quantification up to the maximum goethite content of ~35 wt% (linear correlation with R2 = 0.89). Goethite quantification with CIELAB color parameters was hindered by hematite. In samples with very low or no hematite, goethite quantification was possible with parameters L * 10 (R2 = 0.83) and h ab,10 (R2 = 0.65), also up to ~35 wt% goethite. Consequently, if accurate calibration is possible and depending on mineral mixture components, spectroscopic and CIELAB color parameters should allow goethite quantification in a wide concentration range. • Hematite detectability in mineral mixtures is high due to absorption at 520–560 nm. • Jarosite is also readily detectable due to the combined bands at 390 and 440 nm. • Goethite and jarosite share color characteristics determined with CIELAB parameters. • Hematite modifies CIELAB color characteristics of goethite-jarosite mixtures. • Goethite quantification is possible by spectral and color methods to at least 35 wt%. [ABSTRACT FROM AUTHOR]

The Curiosity rover on Mars, landed in 2012, is capable of mineralogical investigation using X-ray diffraction, complementing the abundant infrared remote sensing data already available on clay minerals. We can, however, expect that the in situ X-ray diffraction information will convey a more complex picture than that inferred from infrared spectroscopy alone. CheMin has landed. [ABSTRACT FROM AUTHOR]

The mechanism of kaolinite transformation into dickite has been investigating using 13 samples from the Frøy and Rind oil fields (Broad Fourteens basin, North Sea), 3 kaolinite specimens with different crystal order (KGa-2, Kaolinite API 17, Keokuk kaolinite), and 2 dickite-rich samples (Natural History Museum collection). Detailed analysis of XRD, thermal analysis, and SEM data show that: (1) as dickite content increases, there is also an increase of the crystal order of kaolinite; (2) in dickite-rich specimens kaolinite and dickite have crystals (or XRD-coherent domains) of the same size; (3) there is no specific dehydroxylation temperature for each polytype, rather particle size and crystal order control dehydroxylation temperature independently of polytype; (4) with progressive dickite content, the development of both particle size and the size of the coherent crystal domains within particles is greater in the c direction than in the a-b plane; (5) the growth of defect-free segments in the c direction is not connected with the growth in the a and b directions, as would be expected in crystallization from solution; (6) textural features indicate coalescence of kaolin plates with burial; (7) there is a very weak positive correlation between particle dimensions and relative kaolinite-dickite content. These results are interpreted as resulting from a double reaction taking place in the solid state with burial. Some kaolinite domains grow in size and crystal order while other domains are transformed into dickite. Presumably, also the dickite domains formed early in the transformation grow in crystal order. The transformation into dickite stops at 90-95% dickite because the remaining kaolinite domains are so large and stable that the stability increase produced by the polytype transformation would be negligible. [ABSTRACT FROM AUTHOR]

The detection of organic molecules associated with life on Mars is one of the main goals of future life-searching missions such as the ESA-Roscosmos ExoMars and NASA 2020 mission. In this work we studied the preservation of 25 amino acids that were spiked onto the Mars-relevant minerals augite, enstatite, goethite, gypsum, hematite, jarosite, labradorite, montmorillonite, nontronite, olivine and saponite, and on basaltic lava under simulated Mars conditions. Simulations were performed using the Open University Mars Chamber, which mimicked the main aspects of the martian environment, such as temperature, UV radiation and atmospheric pressure. Quantification and enantiomeric separation of the amino acids were performed using gas-chromatography-mass spectrometry (GC–MS). Results show that no amino acids could be detected on the mineral samples spiked with 1 µM amino acid solution (0.1 µmol of amino acid per gram of mineral) subjected to simulation, possibly due to complete degradation of the amino acids and/or low extractability of the amino acids from the minerals. For higher amino acid concentrations, nontronite had the highest preservation rate in the experiments in which 50 µM spiking solution was used (5 µmol/g), while jarosite and gypsum had a higher preservation rate in the experiments in which 25 and 10 µM spiking solutions were used (2.5 and 1 µmol/g), respectively. Overall, the 3 smectite minerals (montmorillonite, saponite, nontronite) and the two sulfates (gypsum, jarosite) preserved the highest amino acid proportions. Our data suggest that clay minerals preserve amino acids due to their high surface areas and small pore sizes, whereas sulfates protect amino acids likely due to their opacity to UV radiation or by partial dissolution and crystallization and trapping of the amino acids. Minerals containing ferrous iron (such as augite, enstatite and basaltic lava) preserved the lowest amount of amino acids, which is explained by iron (II) catalyzed reactions with reactive oxygen species generated under Mars-like conditions. Olivine (forsterite) preserved more amino acids than the other non-clay silicates due to low or absent ferrous iron. Our results show that D- and L-amino acids are degraded at equal rates, and that there is a certain correlation between preservation/degradation of amino acids and their molecular structure: alkyl substitution in the α-carbon seem to contribute towards amino acid stability under UV radiation. These results contribute towards a better selection of sampling sites for the search of biomarkers on future life detection missions on the surface of Mars. [ABSTRACT FROM AUTHOR]

This study aims to contribute to a better understanding of the nature and evolution mechanism of interstratified clay minerals. We examined the <2µm or <0.2µm size fraction of interstratified kaolinite- smectite (K-S) formed by hydrothermal and hydrogenic alteration of volcanogenic material from a Tortonian clay deposit (Almería, Spain), a weathered Eocene volcanic ash (Yucatan, Mexico), and a weathered Jurassic bentonite (Northamptonshire, England). The methods used were X-ray diffraction analysis (XRD) of random and oriented preparations, thermogravimetry, chemical analysis, and 29Si MAS nuclear magnetic resonance. The proportions of kaolinite and smectite in K-S (%K) were determined by fitting the XRD patterns of ethylene-glycol-saturated samples with patterns calculated with the NEWMOD computer program. The obtained range of compositions is 0.85%K. A comparison of the results from the various techniques showed non-linear relationships, indicating that the layers in K-S are complex and hybrid in nature. The smectite-to-kaolinite reaction is a solid-state transformation proceeding through formation of kaolinite-like patches within the smectite layers. The process consists of several non-simultaneous stages: (1) removal of parts of the tetrahedral sheet, resulting in formation of kaolinite-like patches; (2) layer collapse to ∼7 Å where the kaolinite-like patches are sufficiently large; (3) Al for Mg substitution in the octahedral sheet, simultaneous or slightly delayed with respect to layer collapse, causing a layer-charge decrease and loss of interlayer cations; (4) Si for Al replacement in the tetrahedral sheet and further loss of interlayer cations. Iron remains in the kaolinite or is lost at the latest stages of the process. [ABSTRACT FROM AUTHOR]